Process for the formation of color photographic images

ABSTRACT

A PROCESS FOR THE FORMATION OF COLOR PHOTOGRAPHIC IMAGES BY PROCESS A MULTI-LAYER TYPE COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL HAING AT LEAST TWO SILVER HALIDE EMULSION LAYERS ON A SUPPORT, WHICH COMPRISES DEVELOPING SAID LIGHT-SENSITIVE MATERIAL IN THE PRESENCE OF A COMPOUND HAVING THE FOLLOWING GENERAL FORMULA 1   R-N&lt;(-Q-C(=S)-)   WHEREIN Q REPRESENTS AN ATOMIC GROUP NECESSARY TO COMPLETE A HETEROCYCLIC RING WHICH MAY BE SUBSTITUTED, AND WHEREIN R IS SELECTED FROM THE GROUP, AN ARYL GROUP, A SUBGROUP, A SUBSTITUTED ALKYL GROUP, AN ARYL GROUP, A SUBSTITUTED ARYL GROUP, AND A HETEROCYCLIC GROUP, IS DISCLOSED.

nited States Patent 3,723,125 PROCESS FOR THE FORMATION OF COLORPHOTOGRAPHIC IMAGES Jun Hayashi, Reiichi Ohi, Tadao Shishido, andTokiharu Kondo, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd.,Kanagawa, Japan No Drawing. Filed Sept. 8, 1970, Ser. No. 70,555

Claims priority, application Japan, Sept. 5, 1969,

44/ 7,068; Apr. 2, 1970, 45/28,712 Int. Cl. G03c 7/00 US. Cl. 9656.2 17Claims ABSTRACT OF THE DISCLOSURE A process for the formation of colorphotographic images by processing a multi-layer type color photographiclight-sensitive material having at least two silver halide emulsionlayers on a support, which comprises developing said light-sensitivematerial in the presence of a compound having the following generalFormula I IL (I) wherein Q represents an atomic group necessary tocomplete a heterocyclic ring which may be substituted, and wherein R isselected from the group consisting of an alkyl group, a substitutedalkyl group, an aryl group, a substituted aryl group, and a heterocyclicgroup, is disclosed.

BACKGROUND OF THE INVENTION (1) Field of the invention The presentinvention relates generally to color photography. More particularly, thepresent invention relates to a process for increasing the color contrastof multi-layer type color photographic light-sensitive materials by theinterimage effect.

(2) Description of the prior art In a multi-layer type colorphotographic light-sensitive material having on a support ared-sensitive emulsion layer, a green-sensitive emulsion layer, and ablue-sensitive emulsion layer, the dye formed by the reaction of theoxidation product of an aromatic amino photographic developing agent anda color former or a coupler generally has the property of absorbing tosome extent other light than the light to be absorbed.

For instance, a magenta dye absorbs blue light and red light to someextent besides the green light to be absorbed. Similarly, a yellow dyeand a cyan dye absorb to some extent light other than the blue light andthe red light respectively to be absorbed.

Such undesirable and unnecessary absorption by the dyes reduces thecolor contrast. Hence, the color obtained tends to become dark and alsothe saturation tends to decrease.

The reduction of the saturation of color by the unnecessary absorptionby the dye can be improved to some extent by the interimageeffect. Theinterimage effect is a phenomenon occurring in a multi-layer type colorphotographic light-sensitive material, wherein the formation of a dyeimage in one emulsion layer influences the formation of the dye image inother emulsion layers. With the interimage effect the color contrast canbe increased.

The interimage effect which increases the color contrast can be definedas follows: A silver halide emulsion layer "ice having red sensitivityand being coupled forming a cyan dye after development is formed on afilm base and a silver halide emulsion layer having blue sensitivity andbeing coupled forming a cyan dye after development is formed on a filmbase and a silver halide emulsion layer having blue sensitivity andbeing coupled forming a yellow dye after development is formed on thered-sensitive emulsion layer. The sample thus obtained is cut into twosamples and one (Sample I) of them is wedge exposed to red light only,while the other sample (Sample II) is exposed to the same amount of redlight and also to blue light capable of causing the same photographiceffect as that due to the red light exposure. Thus, the lowermostred-sensitive emulsion layer only is exposed to the wedge image inSample I, whereas the blue-sensitive emulsion layer and thered-sensitive emulsion layer are exposed to the wedge image in SampleII. After development, the image density of Samples I and II is measuredto observe the contrast of the cyan dye image formed in the redsensitiveemulsion layer. In this case, the interimage effect is said to haveoccurred if the contrast of the cyan dye image in Sample I is higherthan the contrast of the cyan dye image in Sample II. Furthermore, witha multilayer type color photographic light-sensitive material having ona support a red-sensitive emulsion layer, a greensensitive emulsionlayer, and a blue-sensitive emulsion layer, it is possible using thisinterimage effect to increase the contrast of the yellow dye image andthe magenta dye image. The term interimage effect as used in thespecification is intended to encompass this interimage effect capable ofincreasing the color contrast.

This interimage effect is well known in color photography. For instance,W. T. Hanson and C. A. Horton, in Journal of the Optical Society ofAmerica, 42, 663-669 (1952) and A. Thiels, in Zeitschrift fiirWissenschaftliche Photographie, Photophysik and Photochemie, 47, 106-118and 246-255 (1952), describe that the color contrast of a multi-layertype color photographic light-sensitive material is higher when it isexposed to monochromatic light than when it is exposed to white light.The results thereof are that the saturation of the color is increased.

It is known that this interimage effect is important for increasing thecolor contrast but the manner of increasing this interimage effect isnot well known. For instance, it is known that the interimage effect canbe caused by using a coupler capable of releasing a developmentinhibitor, such as benzotriazole, a mercapto compound, and the like, atcoupling or a compound such as hydroquinone, and the like, which canrelease an inhibitor such as iodine ion, a mercapto compound, and thelike, at development. However, since such compounds are unstable and arereadily decomposed or since such compounds greatly reduce thesensitivity of the light-sensitive material, the use of these compoundsis limited. Accordingly, hitherto increasing the color contrast by theinterimage effect using such known compounds without adversely affectingthe other photographic properties has been diflicult.

Therefore, an object of the present invention is to provide a colorphotographic image in which unnecessary absorption by dyes is correctedby the interimage effect.

Another object of this invention is to provide a color photographicimage having a high saturation unaccompanied with a reduction insensitivity.

SUMMARY OF THE INVENTION As the results of various studies, theinventors have discovered that at the development of a multi-layer typecolor photographic light-sensitive material having at least two silverhalide photographic emulsion layers, the interimage eifect occursmarkedly if the light sensitive material is developed in the presence ofa compound represented by the general Formula I wherein Q represents anatomic group necessary for forming a heterocyclic ring, which may besubstituted, and R represents an unsubstituted or a substituted alkylgroup, an unsubstituted or a substituted aryl group, or a heterocyclicring group.

DESCRIPTION OF THE INVENTION In general Formula I, Q represents thenecessary atomic group for forming a heterocyclic ring, which may besubstituted. For example, the thiazolidine-Z-thion ring series, such asthiazolidine-Z-thion ring, 4-methyl-thiazolidine-2- thion ring, and thelike; the imidazolidine-Z-thion ring series, such as1,3-dimethylimidazolidine-Z-thion ring, a 1,3-dimethylimidazolidine-2-thion ring, and the like; theselenazolidine-Z-thion ring series, such as a selenazoline-Z- thionring, a 4-methylselenazolidine-Z-thion ring, and the like, the1,3,4-thiadiazoline-2-thion ring series, such as al,3,4-thiadiaZoline-2-thion ring, a 5-methyl-l,3,4-thiadiazoline 2-thionring a S-ethylthio-1,3,4-thiadiazoline-2- thion ring, a5-[2-(4-phenyl-5-thio-1,3,4-thiadiazoline-2- yl) mercaptoethylthio]1,3,4-thiadiazoline-2-thion ring, and the like; thel,3,4-selenadiazoline-Z-thion ring series, such as a1,3,4-selenadiazoline-Z-thion ring, 5-ethyl-1,3,4-selenadiazoline-Z-thion ring and the like; the 4-thiazoline- 2-thionring series, such as a 4 methyl-4-thiazoline-2- thion ring, a4-phenyl-4-thiazoline2-thion ring, a 4-methyl5-ethoxycarbonyl-4-thiazoline-2-thion ring, a 4,5-trimethylenethiazoline2-thion ring, a 4,5-tetramethylenethiazoline-Z-thion ring, and the like;the 4-selenazoline-2- thion ring series, such as a4-selenazoline-2-thion ring, a 4-methyl-4-selenazoline-2-thion ring, a4-phenyl-4-selenazoline 2-thion ring, a 5-ethylthio-1,3,4-thiadiazoline-2- 2-thion ring series such as a1,Z-dihydropyridine-Z-thion ring, a 6-ethyl-1,2-dihydropyridine-2-thionring, and the like, the benzthiazoline-Z-thion ring series, such as abenzthiazoline-Z-thion ring, a 6-methyl-benzthiazoline-Z-thion ring, a6-ethylbenzthiazoline-Z-thion ring, a 6-methoxybenzthiazoline 2 thionring, a 6-chlorobenzthiazoline-2- thion ring, aS-methylbenzthiazoline-Z-thion ring, and the like; thebenzoxazole-Z-thion ring series, such as benzoxazoline-2-thion ring, a6ethylbenzoxazoline-2-thion ring, a 6-methoxybenzoxazoline-Z-thion ring,a S-methylbenzoxazoline-Z-thion ring, and the like; thebenzimidazoline-Z- thion ring series, such as1,3-dimethylbenzimidazoline-2- thion ring a1,3-di-n-propylbenzimidazoline2-thion ring, a1,3-di-n-deeylbenzimidazoline-Z-thion ring, a1,3-dibenzylbenzimidazoline-Z-thion ring, a5-chloro-1,3-dimethylbenzimidazoline 2-thion ring, a5-methyl-1,3-di-benzylbenzimidazoline-Z-thion ring, and the like; thebenzselenazoline Z-thion ring series, such as a berlzselenazoline-Z-thion ring, a 6 ethylbenzselenazoline-2-thion ring, a 6-methoxybenzselenazoline-Z-thion ring, a -chloro-benzselenazoline-Z-thionring, and the like; and the 1,2-dihydroquinoline-Z-thion ring series,such as a 1,2-dihydroquinoline-2-thion ring, a6-methyl-1,2-dihydroquinoline-Z-thion i'ing, a6-chloro-l,Z-dihydroquinoline-Z-thion ring, and the ike.

R in general Formula I represents an unsubstituted alkyl group or ahydroxyl group-, an aryl group-, or a morpholino group-substitued alkylgroup having from 1 to 6 carbon atoms, such as a methyl group, an ethylgroup, a propyl group, a hexyl group, a decyl group, a hydroxyethylgroup, a benzyl group, a morpholinoethyl group, and the like; anunsubstituted aryl group or an alkyl group, an alkoxyl group-, or ahalogen atom-substituted aryl group, such as a phenyl group, a2-methylphenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group,and the 4 like; or a heterocyclic ring group such as a 2-pyridyl group,and the like.

When R in general Formula I is a hydrogen atom, the hydrogen atom isenolated to provide a mercapto type compound. Such compounds having themercapto group generally strongly inhibit the development of silverhalide and frequently causes a reduction in sensitivity.

On the other hand, when the N-position is substituted as in the compoundof this invention shown by general Formula I, no mercapto-type group isformed. Hence, a high interimage effect can be obtained without greatlyreducing the sensitivity.

Although the mechanism of obtaining the interimage effect by thecompound of this invention is not clearly understood, it is believedthat the following explanation is applicable. The compound of thisinvention can diffuse through a hydrophilic colloid and hence it isconsidered that the compound can diffuse between each emulsion layer ofa multi-layer type photographic light-sensitive material. Thus, when thecompound is added, for instance, to the emulsion, it is first adsorbedby the silver halide crystals where it is fixed and hence it isimpossible for it to diffuse freely into adjacent emulsion layers.However, the compound is released at the development of the silverhalide and diffuses into the adjacent emulsion layers, inhibiting thedevelopment there. Accordingly, if a compound is strongly adsorbed onthe silver halide particles (for example, a compound of the generalFormula I in which, however, R is a hydrogen atom), a desensitizationoccurs severely, whereas when the adsorption of a compound by the silverhalide particles is too weak, no interimage elfect is obtained.

Therefore, the compound of this invention is believed to have excellentcharacteristics in that an effective interimage effect can be obtainedwithout seriously causing desensitization.

Among the compounds represented by general Formula I, the compoundrepresented by the general Formulae Ia, Ib, and Ic shown below giveparticularly less desensitization and better results;

A C=s ,l

wherein X represents a sulfur atom, an oxygen atom, a selenium atom, aNR" group, or a CH=CH group; wherein A and B each represents a hydrogenatom, an unsubstituted or a substituted alkyl group, an unsubstituted ora substituted aryl group, an alkoxycarbonyl group, an acyloxy group, oran atomic group necessary to complete a saturated or unsaturated ringhaving from 5 to 6 carbon atoms, which may be substituted, by thecombination of the groups A and B; wherein Y represents an alkyl group,an alkoxyl group, or an alkylthio group; and wherein R and R" have thesame meanings as R described above in regard to general Formula I.

Each of the groups A and B in general Formula Ia represents a hydrogenatom; an unsubstituted or a hydroxyl groupor a halogen atom-substitutedalkyl group having from 1 to 6 carbon atoms, such as a methyl group,

an ethyl group, a butyl group, a hydroxyethyl group, a 2-chloroethylgroup, and the like; an unsubstituted or an alkyl group-, a hydroxylgroup or a halogen atom-substituted group, a '3-chlorophenyl group, andthe like; an

group, such as a phenyl group, and the like; an alkoxyl group such as amethoxy group, an ethoxy group, and the like; or a halogen atom, such asa chlorine atom, a bromine atom, and the like, and vice versa.

alkoxycarbonyl group such as an ethoxycanbonyl group; 5 Moreover, Y inthe general Formula Ic represents an aryloxy group such as apropanoyloxy group, and the an alkyl group, such as a methyl group, anethyl group, like; and group A combined with group B represents an ann-butyl group, an n-hexyl group, and the like, an atomic group necessaryto complete an unsaturated ring alkoxyl group, such as a methoxy group,an ethoxy group, having from 5 to 6carbon atoms, .such asa trimethyleneand the like, or an alkylthio group such as a methylthio group, atetramethylene group, and the like; or an atomic 10 group, an ethylthiogroup, a 2-(4-phenyl 5 thi0-1,3,4- group necessary to complete anunsubstituted benzene ring thiadiazoline-Z-yl) mercaptoethylthio group,and the like. or a benzene ring substituted with an alkyl group, suchExamples of the compounds which can be employed in as a methyl group, anethyl group, and the like; an aryl this invention are shown below:

Compound 1...- S\ M.P. 90 0.

0:8 N (EH1 Compound 2.; S\ M.P. 76 C.

. C=S hHl Compound 3... S\ M.P. 74 C.

/C=S \N nzHr Compound 4... 8 MP. 55 C.

:8 N lso-hHu Compound 5-.. S\ M.P. 149 C.

Compound 6- S M. P. 190 C.

CHI

/C=S N Compound 7-.. 8 MP. 87 C.

/C=S N 6H3 Compound 8-.. S M.P. 130 0.

Compound 9..- H: 8 M1. 81-82 C.

H C=s Compound 10-- H: 3 MP. 102 0.

C=S H: H:

Compound 11: S\ M.P. 96 C.

Compound 12..- S\ M.P. 114 C.

1 c=s OH;

Compound 13.; S M.P. 162 C.

HECIOOC I CH3 Compound 14.: 8 MP. 82 C C=S CH1 Compound 15.. S\ MP. 119C:

Compound 16.. S MsP. 166 0.

OCH:

Compound 17..

Compound 18.. 0

Compound 19... 0

Compound 20... Se

Compound 23... nCnHn Com ound 24.:

Com und 25..

M.P. 113 C;

M.P. 133 C;

M.P. 92 C:

M.P. 80 Cu IVLP: 151 C;

Llquldl Compound 26..- c G M1. 143 C.

Compound 27.. Ml. 118 C.

S N (5H;

Compound 28.. O1 1 MP. 184 C.

Compound 29.. MP. 94 C.

Compound 30.- Ml. 90 C.

N (EH3 Compound 31-- M. P. 46 C.

N hHu Compound 32.. 8 MP. 123 C.

Compound 33.. (311: MP. 62.5 C.

Compound 34..

Compound 35-. M.P. 108 C.

s mots-IE \C S Compound 36-.

Compound 37..

H.C L AH.

Compound 38... S

Eho/ Tsomoms-f \c=s M.P. 66 C.

M-P; 152 C.

M.P. 145 C.

The compounds illustrated above can be prepared by well known methods.Hereinafter, examples of the synthesis of the compounds shown above areas follows:

Synthesis-1 (Compounds 1-8) Compounds 1-8 illustrated above can beprepared by the method described in Journal of The Chemical Society,473-476 (1939), using Z-mercaptobenzthiazole as the starting material.

Synthesis-2 (Compounds 9-17) Compounds 9-17 shown above can be preparedby the method shown in Journal of The Chemical Society, 1503- 1509(1949), by the reaction of a dithiocarbamate and an alpha haloketone.

Synthesis-3 (Compounds 18 and 19) Compounds 18 and 19 illustrated abovecan be prepared by the method described in Journal of The ChemicalSociety, 143-151 (1939).

Synthesis-4 (Compound 20) Compound 20 can be prepared by the methoddescribed in Journal of The Chemical Society, 1762-1766 (1939).

Synthesis-5 (Compound 21) Compound 21 can be prepared by the methoddescribed in Nippon Yakugaku Zasshi (Journal of Pharmaceutical Societyof Japan), 1865-1369 (1954).

Synthesis-6- (Compound 22) The 2-propylthiobenzimidazole, obtained byrefluxing under heating for 6 hours Z-mercaptobenzimidazole and anequimolar amount of propyl iodide in ethanol, is refluxed under heatingfor 12 hours together with an equimolar amount of propyl iodide indioxane. After distil1-' Analysis as C H N S. Found (percent): C, 66.75;H, 7.63; N, 11.42. Calculated (percent): C, 66.64; H, 7.74; N, 11.96.

Synthesis-7 (Compounds 23-26) Compounds 23-26 can also be prepared byprocedures similar to the procedure described in Synthesis-6.

Synthesis-8 (Compounds 27-29) Compounds 2 7-29 can be prepared accordingto the method shown in Berichte der Deutschen Chemischen Gesellschaft,33, page 3359 and ibid, 35, page 3682.

Synthesis-9 (Compound 30) Compound 30 can be prepared by the methodshown in Justus Lierbigs Annalen der Chemie, 331, page 245.

Synthesis-10 (Compounds 31 and 33) Compounds 31 and 33 can be preparedby the method shown in Journal of Organic Chemistry, 14, page 946.

Synthesis-11 (Compound 32) 6.5 g. of thiazoline-Z-thion is mixed with4.5 cc. of 37% formalin at 50 C. and then an alcohol solution of 5 g. ofmorpholine is added gradually to the mixture, whereby white crystals areformed. By recrystallizing the crystals from alcohol, 9 g. of thecrystals of Compound 32 having a melting point of 123 C. is obtained.

Synthesis-12 (Compounds 34, 36 and 38) Compounds 34, 36 and 37 can beprepared according to the methods taught in Journal fiir PraktischeChemie, 60, page 53 and ibid, 60, pages 187-188.

Synthesis-13 (Compound 35) Compound 35 can be prepared by the methoddescribed in Berichte der Deutschen Chemischen Gesellschaft, 27, page2513.

Synthesis-14 (Compound 37) Compound 37 shown above can be preparedaccording to the method described in Chemical Abstracts, 33, page 25 18.

By incorporating the compound of this invention represented by generalFormula I in a multi-layer type color photographic light-sensitivematerial, it can be incorporated in at least one of the layersconsisting of the silver halide emulsion layers of a multi-layer typecolor photographic light-sensitive material and the layers adjacent tothe silver halide emulsion layers, such as a yellow filter layer, anantihalation layer, intermediate layers, and a protective layer.Furthermore, the compound can be incorporated in a developer solutionfor the multi-layer type color photographic light-sensitive material.Still further, the above two modes of the addition of the compound canbe used in combination.

The amount of the compound used in this invention varies depending tothe nature of the mult-i-layer type color photographic light-sensitivematerial to be employed and also the manner of development but theamount generally ranges from 0.006 to 1.5 g. per mole of silver halidewhen the compound is incorporated in the silver halide emulsion layer ofa multi-layer type color photographic light-sensitive material, from0.006 to 1.5 g. per 100 g. of gelatin when it is incorporated in a layeradjacent to the above-mentioned silver halide emulsion layer, andfurther, from 0.1 mg. to 1 g., preferably from mg. to 500 mg. per literof developer solution when the compound is added to the developersolution. However, the ranges set forth above for this compound are notto be interpreted as limiting.

As a solvent for incorporating the compound of this invention a solventwhich does not adversely affect the silver halide photographic emulsion,such as water, methanol, and acetone, can be used.

In incorporating the compound of this invention in a developer solution,any developer solutions which can reduce silver halide particles tosilver can be employed. For instance, in case of black and whitedevelopment, a developer solution containing polyhydroxybenzenes,N-alkylaminophenols, 1-phenyl-3-pyrazolidones, or a mixture thereof, asthe developing agent, can be used. As the polyhydroxybenzene, suitableones are, for example, hydroquinone, pyrocatechol, pyrogallol, and thelike; as the N- monoalkylaminophenol, suitable ones areN-methylaminophenol, N-ethylaminophenol, and the like; and as the 1-phenyl-3-pyrazolidone, suitable ones are l-phenyl-3-pyrafclxilidone,1-pheny1-4,4-dimethyl-3-pyrazolidone, and the Moreover, in case of colordevelopment, the compound of this invention can be added to a developersolution containing, as a developing agent, a p-phenylenediaminederivative, such as 4-amino-N,N-diethylaniline, 4-amino-S-methyI-N-methyl-N-(beta methylsulfone amidoethyl) aniline,4-amino-3-methyl-N-ethyl-N-(beta-hydroxyethyl) aniline, and the like.

In increasing the interimage effect by the present invention, themulti-layer type color photographic light-sensitive material can beprocessed at ordinary processing temperatures, i.e., at from to C. butcan be processed at higher temperatures, i.e., at 30 to 80 C. or at aneven higher temperature, if desired.

The compound of this invention can be used in any processes capable offorming color photographic images, that is to say, in processes fordeveloping multi-layer type color photographic light-sensitive materialshaving at least two photographic silver halide emulsion layerscontaining silver halide dispersions in hydrophilic colloids to form dyeimages according to the reduced ratio of silver halide into silver. Forinstance, better results are obtained when the compound of thisinvention is used in the so-called reversal color photographic process,i.e., a process wherein, after exposing a multi-layer color photographiclightsensitive material having at least two silver halide photographicemulsion layers sensitized to different wavelength regions,respectively, the light-sensitive material is first developed in a blackand white developer solution to provide a negative silver image and thenthe silver ha- 16 lide particles in the areas which have not beendeveloped in the black and white development are developed by a colordeveloper solution to provide positive dye images.

AS the reversal color photographic process, there are the so-calledcoupler-in-developer type color system, wherein a dye image is formed bysuccessively developing a multi-layer type color photographiclight-sensitive material using color developer solutions each containinga diffusible coupler to be coupled in each difierent color, and theso-called coupler-in-emulsion layer color system wherein a dye image isobtained by incorporating each diffusion resisting coupler capable ofbeing coupled in each different color in each silver halide emulsionlayer of the multi-layer type color photographic light-sensitivematerial and processing the light-sensitive material by color developersolutions containing no couplers.

The compound of this invention can be used effectively in both systemsof the reversal color photographic processes.

Moreover, the compound of the present invention can also be used in asystem wherein a negative dye image is obtained by developing amulti-layer type color photographic light-sensitive material having atleast two silver halide photographic emulsion sensitized to differentWavelength regions, each containing a diffusion resistant coupler,directly after exposure in a color developer solution.

Also, the compound of this invention can be used in the color diffusiontransfer process, as described in the specifications of US. Pats.2,559,643, 2,698,798, and 3,227,551, having the characteristics that adeveloper solution, a coupler, or a dye is diffused from alight-sensitive layer to a reception layer in contact with thelightsensitive layer in proportion to the images in the lightsensitivelayer.

Still further, the compound of this invention can be used in the silverdye bleaching color photographic process, as described in thespecifications of U8. Pats. 2,020,- 775 and 2,410,025, in which a dyeimage can be obtained by bleaching the dye in the areas containingsilver.

In the multi-layer type color photographic light-sensitive material tobe used in the present invention it is desirable to apply ared-sensitive silver halide photographic emulsion layer, agreen-sensitive silver halide photographic emulsion layer and ablue-sensitive silver halide photographic light-sensitive emulsion layerto a support in this order.

Also, it is desirable that in the multi-layer type lightsensitivematerial used in this invention after development, cyan, magenta, andyellow images are formed in the red-sensitive, green-sensitive, andblue-sensitive silver halide photographic emulsion layers, respectively.However, other emulsion layer orders and other methods for forming dyeimages than those described above can be employed in this invention.

As the silver halide emulsion used in this invention, there are employedphotographic emulsions containing silver halides such as silver bromide,silver iodide, silver chloride, silver chlorobromide, silveriodobromide, and silver chloroiodo bromide. In particular, betterresults are obtained in employing at least a photographic emulsion layercontaining, silver chloroiodide, silver iodobromide, or silverchloroiodobromide having an iodine content of from 1 to 10 molarpercent.

Furthermore, the silver halide photographic emulsion to be used in thepresent invention can be chemically sensitized by methods well known inthis field, such as, by using a compound containing an unstable sulfur,such as sodium thiosulfate, allylthiocarbazide; a gold compound such asa gold (I) complex salt of thiocyanic acid; a reducing agent such asstannous chloride; or a polyalkylene oxide derivative. Also, the silverhalide photographic emulsion to be used in the present invention can bespectrally sensitized using a cyanine dye, such as 1,1'-diethylcyanineiodide, 1,1'-diethyl-9-methylcarbocyanine bromide,anhydro-5,5'-dipl1enyl-9-ethyl-3,3'-di(2-sulfoethyl)-'benzoxazolocarbocyanine hydroxide, and the like, used alone or incombinations thereof. Still further, the silver halide photographicemulsion to be used in this invention can contain a developing agentcapable of releasing a developing inhibitor, such as2-iodo-S-pentadecylhydroquinone or2-methyl-5-(1-phenyl-5-tetrazolylthio)-hydroquinone; a stabilizer, suchas 4-hydroxy- 6 -methyl- 1,-3,3a,7 tetraazaindene, benz'imidazole, or 1phenyl-- mercaptotetrazole; a hardening agent, such as formaldehyde ormucobromic acid; and a wetting agent, such as saponin or sodiumalkylbenzenesulfonate.

The invention now will be explained in greater detail by reference tothe following examples. In the following examples, two types of colorphotographic processes are used. That is to say, the so-calledcoupler-in-developertype color system, wherein couplers are suppliedfrom color developer solutions, and the so-called coupler-inemulsionlayer type system wherein couplers are incorporated into thephotographic emulsion layers of a color photographic light-sensitivematerial, are employed.

'In the following examples, in the coupler-in-developer type colorsystem the multi-layer type color photographic light-sensitive materialhaving the following composition is used.

Coupler-in-Developer Type Color System To a cellulose triacetate filmbase were applied successively the following different emulsion layers:

First layer-Red-sensitive silver halide emulsion layer: A layer formedby coating a high speed gelatino silver iodobromide emulsion having redsensitivity due to a sensitizing dye and containing no coupler so thatthe amount of silver is 15 mg./1'00 cm.

lSecond layerGreen-sensitive silver halide emulsion layer: A layerformed by coating a high speed silver iodobromide emulsion having greensensitivity due to a sensitizing dye and containing no coupler so thatthe amount of silver is 15 mg./ 100 cm.

Third layerYellow filter layer: A layer formed by coating a yellowcolloidal silver dispersion containing colloidal silver in gelatin sothat the amount of silver is 2.5 mg./100 cm.

Fourth layer--Blue-sensitive silver halide emulsion layer: A layerformed by coating a high speed silver iodobromide emulsion having bluesensitivity and containing no coupler so that the amount of silver is 20mg./ 100 cm Also in the examples shown 'below relating to thecoupler-in-developer type color system, the multi-layer typephotographic light-sensitive material was processed using the followingprocedures:

Process: Time (min.) (1) Hardening bath 1 (2) Water washing 2 (3)Negative development 4 (4) Water washing 3 (5) Reversal red flashexposure (6) Cyan color development 4 (7) Water washing 3 (8) 'Reversalblue flash exposure (9) Yellow color development 4 (10) Water washing 3(11) Reversal white exposure (12) Magenta color develpoment 4 (13) Waterwashing 3 (14) Silver bleaching 3 (15) Fixing 3 (16) Water washing anddrying The temperatures of the processing baths in the above processwere 27 C. The composition of the baths are as shown below:

18 Hardening bath Sodium hexametaphosphate g 2.0 Sodium bisulfite g 5.0Sodium pyrophosphate (10H O) g 15.0 Sodium sulfate g 100.0 Potassiumbromide g 2.0 Sodium hydroxide ..g 0.1 37% formaldehyde cc 17.0 Wateradded to make the total volume to 1000 cc.

Negative developer solution N-methyl-p-aminophenol sulfate g 5.0 Sodiumsulfite a g 79.0 Hydroquinone g 2.0 Sodium hydroxide n. n g 1.0 Sodiumcarbonate (H O) g 41.0 0.1% potassium iodide cc 12.5 Potassium bromide g3.6 Sodium hydroquinone monosulfonate g 4.0 Potassium thiocyanate g 2.00.5% 6-nitrobenzoindazole nitrate cc 5.0 Water added to make the totalvolume to 1000 cc.

Cyan color developer solution Potassium bromide g 2.9 1%-nitrobenzoimidabole nitrate cc 3.0 0.1% potassium iodide -..cc.... 11.0Sodium sulfite g 10.0 Sodium sulfate g 60.0 Potassium thiocyanate g 1.24-amino-3-methyl-N ethyl-N-(betahydroxyethyl)- aniline sulfate 3 2.5Sodium hydroxide g 3.4 1-hydroxy-N-(2propionamidophenethyl)-2-naphthamide g 1.5 2,4-dichloro-1-naphthol -g0.2 2-methyl-2,4-pentane diol cc 10.0 Polyoxyethylene-methylphenyl ether0.5 Monobenzyl-p-aminophenol hydrochloride g 0.4 p-Aminophenolhydrochloride g 0.12 Water added to make the total volume to 1000 cc.

Yellow color developer solution Sodium sulfite g 10.0 Potassium bromideg 0.65 0.1% potassium iodide cc 29.0 1% 6-nitrobenzoimidazole nitrate cc10.0 Sodium sulfate t cc 64.0 N,N diethyl p phenylenediaminehydrochloride g 3.0 Sodium hydroxide g 2.4 2-methyl-2,4-pentanediol cc20.0 2-benzoyl-2-methoxyacetanilide g 1.8 Diethyl hydroxylamine cc 0.3Polyoxyethylene-methylphenyl ether g 0.8 Water added to make the totalvolume to 1000 cc.

Magenta color developer solution Conc. sulfuric acid cc 2.0 Sodiumphosphate (12H O) g 40.0 Sodium sulfite g-.. 5.0 Potassium thiocyanate g1.2 0.1% potassium iodide cc 7.5 Potassium bromide g 0.64-amino-3-methyl-N-ethyl N (beta-methylsulfonamidoethyl)-aniline sulfateg 2.0 Ethylene diamine cc 6.0 Sodium hydroxide cc 0.3 1-(2,4,6trichlorphenyl) 3 (4-nitroanilino)-5- pyrazolone g 1.72-methyl-2,4-pentanediol cc 10.0 Sodium sulfate g 50.0Polyoxyethylene-methylphenyl ether g 0.5 Water added to make the totalvolume to 1000 cc.

19 Bleaching solution Potassium ferricyanide g 100.0 Potassium bromide g30.0

Water added to make the total volume to 1000 cc.

Fixing solution Sodium thiosulfate g 125.0 Sodium sulfite g 9.0 Wateradded to make the total volume to 1000 cc.

Furthermore, in the following examples, in the couplerin-emulsion layertype color system, a multi-layer type color photographic light-sensitivematerial having the following composition is used.

Coupler-in-emulsion layer type color system To a cellulose triacetatefilm base are successively applied the following different emulsionlayers.

First layer-Antihalation layer: A layer formed by coating a graycolloidal silver dispersion containing colloidal silver in gelatin sothat the amount of silver is 3 mg./100 cm.

Second layer-Intermediate layer: A layer formed by coating gelatin in anamount of 13.4 mg./100 cm.

Third layer-Red-sensitive silver halide emulsion layer: A layer formedby coating a high speed gelatino silver iodo-bromide emulsion layerhaving red sensitivity due to a sensitizing dye and containing a cyancoupler, (a coupler emulsion prepared by dissolving a cyan coupler,1-hydroxy-4-chloro-N-dodecyl-2-naphthamide in tricresyl phosphate anddispersing the solution in gelatin) so that the amount of silver is 10mg./100 cm.

Fourth layer-Intermediate layer: A layer formed by coating gelatin in anamount of 13.4 mg./ 100 cmf Fifth layer-Green-sensitive silver halideemulsion layer: A layer formed by coating a high speed gelatino silveriodo-bromide emulsion having green sensitivity due to a sensitizing dyeand containing a magenta coupler (a conpler emulsion prepared bydissolving a magenta coupler, 1-(2,6-dichloro-4-methoxyphenyl)-3-[3{alpha-(2,4-ditert-amylphenoxy)propionamido}benzamido] 5 pyrazolone indibutylphthalate and dispersing the solution in gelatin) so that theamount of silver is 15 mg./100 cm.

Sixth layerYellow filter layer: A layer formed by coating a yellowcolloidal silver dispersion prepared by dispersing colloidal silver ingelatin so that the amount of silver is 2.5 mg./100 cm.

Seventh layerBlue-sensitive silver halide emulsion layer: A layer formedby coating a high speed gelatino silver iodobromide emulsion containinga yellow coupler (a coupler emulsion prepared by dissolving2-benz0yl-2'- chloro 5 tridecanoyloxyacetanilide in dibutylphthalate anddispersing the solution in gelatin) so that the amount of silver in thecoated layer is 15 mg./ 100 cm.

Eighth layer-Protective layer: A layer formed by coating :1 gelatin inan amount of 8.9 mg./100 cm.

In the coupler-in-emulsion layer type color system in the followingexamples, the multi-layer type color photographic light-sensitivematerial was processed using the following procedures:

The temperatures of the above-described processing baths in theprocedure were 30 C. The compositions of the processing baths were asshown below:

20 Hardening bath Sulfuric acid (1:1) cc 5.4 Sodium sulfate g 150.0Sodium acetate g 20.0 30% pyruvaldehyde cc 40.0 37% formaldehyde cc 20.0Water added to make the total volume to 1000 cc.

First developer solution N-methyl-p-aminophenol sulfate g 2.0 Sodiumsulfite g 90.0 Hydroquinone g 8.0 Sodium carbonate (1H O) g 52.5Potassium bromide g 5.0 Potassium thiocyanate g 1.0 Water added to makethe total volume to 1000 cc.

Secondary developer solution Benzyl alcohol cc 5.0 Sodium sulfite g 5.0Hydroxylamine hydrochloride g 2.0 3-methyl 4amino-N-ethyl-N-(beta-methylsulfonamidoethyl)aniline sulfate g 1.5Potassium bromide g 1.0 Sodium phosphate g 30 Sodium hydroxide g 0.5Ethylene diamine (70% aqueous solution) cc 7 Water added to make thetotal volume to 1000 cc.

Bleaching solution Ferricyanide g Sodium acetate g 40 Glacial aceticacid g 20 Potassium bromide g 30 Water added to make the total volume to1000 cc.

Fixing solution Sodium thiosulfate g Sodium acetate g 70 Sodium sulfitet g 10 Potassium alum g 20 Water added to make the total volume to 1000cc.

EXAMPLE 1 According to the above-described technique, two types ofmultilayer type color photographic light-sensitive materials forcoupler-in-developer type color system were prepared.

One of them was prepared as a control sample and the second one has thesame composition as the control sample except that Compound 2 describedhereinbefore was incorporated in the first emulsion layer, the secondemulsion layer, or the fourth emulsion layer of the lightsensitivematerial in an amount of 100 mg. per mol of silver halide.

Each of the multi-layer type color photographic lightsensitive materialsthus prepared was subjected to the following two types of sensitometricexposure, i.e., red exposure alone and white exposure (red light+greenlight-l-blue light). In the two types of exposures the amount of redlight in the former was controlled to be the same as the amount of redlight in the latter and further the amount of each component of thegreen light and the blue light in the white light was controlled toprovide the same photographic effect as that with the red light.

Each of the samples thus exposed was developed according to thedeveloping procedure as described above for the coupler-in-developertype color system. After development the density of the cyan dye in eachsample was measured and expressed as a function of the red exposureamount. The interimage effect of each sample can be evaluated using theratio of gamma values of the characteristic curves of the cyan dyeimages exposed to red light alone and exposed to white light (7 /7wherein 21 7 represents the gamma value of the cyan dye image when thesample is exposed to red light, while represents the gamma value of thecyan dye image when the sample is exposed to white light. Also, theinterimage effeet can be evaluated by the difference in sensitivityobtained at the density value at D=0.6, i.e., A log E [A log E: (log Eat D=0.6 of the cyan dye image when exposed to white light)-(log E atD=0.6 of the cyan dye image when exposed to red light)]. In other words,if the interimage effect to the cyan dye image is larger, the ratio 'y/'y is higher and also A log E becomes larger.

The results obtained are shown in Table 1.

1 MgJmol of silver halide.

The results in Table 1 show clearly that by incorporating Compound 2 inthe emulsion layers, the values of /y and A log E are increased andhence the interimage effect is increased.

EXAMPLE 2 According to the abovedescribed procedure, 41 types ofmulti-layer type color photographic light-sensitive materials forcoupler-in-developer type color systems were prepared. One of them wasprepared as a control sample with the others having the same compositionas the control sample except that each of the compounds of thisinvention, shown in Table 2, was incorporated in the bluesensitivesilver halide photographic emulsion layer (the above-described fourthlayer) of each of the samples in the amount shown in the same table.Each of the multilayer type color photographic light-sensitive materialsthus obtained was exposed and developed using the same procedures as inExample 1 and also the ratio 'y /y was obtained by measuring thedensity.

On the other hand, in order to determine the influence of the compoundsshown in Table 2 on the sensitivity of the blue-sensitive emulsion layerof the multi-layer type color photographic light-sensitive material, itwas sensitometrically exposed to blue light and then processed accordingto the developing procedures of the coupler-indeveloper type colorsystem, thereafter the density of the yellow dye image was measured. Bythe variation of the sensitivity value S (expressed as a relative valuewith the sensitivity value of the control sample being assumed to be100) obtained at D=0.6, the extent of the compound reducing thesensitivity of the blue-sensitive emulsion layer can be determined. Thatis to say, a lower sensitivity value shows that the compoundincorporated reduced the sensitivity of the blue-sensitive emulsionlayer to a greater extent. The values of 'y /'y and the sensitivityvalues S thus obtained are shown in Table 2 in which the values are alsoshown at the same time, for the sake of comparison, for the twocomparison compounds X and Y, shown below:

Compound X (for comparison) Compound Y (for comparison) In Table 2,shown below, the developing procedures were conducted separately inExperiments No. 1 to No. 4. To make it possible to compare ExperimentsNo. l to 4, a control experiment was conducted in each experiment (theresults of the control experiment are shown at the beginning of eachexperimental group). That is to say, each control experiment was soconducted that essentially the same results were obtained and hence theresults of the experimental groups can be compared directly with eachother.

TABLE 2 Compound Amount 1 'yR/'yw S 1 Experiment No. 1:

ontr 0 1. 14 100 6 1. 19 101 60 1. 48 110 600 2. 15 105 1500 1. 98 98200 1.35 98 400 1.80 200 1.40 100 400 1. 89 98 200 1. 21 400 1. 39 89Control 0 1. 12 100 200 1. 38 86 400 1. 68 66 200 l. 28 79 400 1. 48 61200 1. 35 77 400 l. 48 60 200 1. 30 58 400 1. 49 30 200 1. 21 55 400 1.28 38 1 Mg./mol of blue-sensitive silver halide. Relative. sensitivityof blue-sensitive layer.

From the results shown in Table 2, it can be seen that by incorporatingCompounds 1-17 of this invention, the values of 'y /7 become markedlylarger and hence the interimage effects are increased.

Also, from the results shown in Table 2,'it is clear that when thecompound of general Formula I, wherein, however, R is a hydrogen atom,i.e., Compound X or Y which can assume a mercapto form on enolation, thevalue of 'y /v becomes larger but the sensitivity is greatly reduced.

As shown above the compounds of this invention have the advantages ofincreasing the interimage effect without causing desensitization to agreat extent.

EXAMPLE 3 A multi-layer type color photographic light-sensitive materialfor the coupler-in-developer type color system was subjected to fourtypes of sensitometric exposures, i.e., red light, green light, bluelight, and white light (red light-l-green light+blue light) separately.The amount of each of the red light, the green light, and the blue lightin the white light was same as that of the red light, the green lightand the blue light respectively when the light-sensitive material wasexposed to each component alone. Also, each of the red light, the greenlight and the blue light was controlled so that the same photographiceffect was provided.

Several groups of the thus exposed four samples were prepared and eachof the groups of the four samples was developed according to theabove-described developing procedures for the coupler-in-developer typecolor system except that the negative developer solution containsCompound 3. After development, the ratio 'y /'y of the gamma values ofthe characteristic curves of the cyan dye images in the case of exposureto red light and in the case of exposure to white light, the ratio v /vof the gamma values of the characteristic curves of the magenta dyeimages in the case of exposure to green light and in the case ofexposure to white light, and the ratio 'y /'y of the gamma values of thecharacteristic curves of the yellow dye images in the case of exposureto blue light and in the case of exposure to white light were obtained.The results obtained are shown in Table 3.

1 Mg./liter of developer solution.

From the results shown in the above table, it can be seen that byincorporating Compound 3 in the negative developer solution, theinterimage effect was increased in the yellow dye layer, magenta dyelayer and cyan dye layer.

EXAMPLE 4 According to the above-described procedures for thecoupler-in-emulsion layer type color system, 11 types of multi-layertype color photographic light-sensitive materials were prepared. One ofthem was prepared as a control sample and the remaining ten had the samecomposition as the control sample except that Compound 1 wasincorporated in either the protective layer (the eighth layer), theblue-sensitive silver halide emulsion layer (the seventh layer), theyellow filter layer (the sixth layer), or the intermediate layer (thefourth layer) as shown in Table 4 and in the amount shown in Table 4.

The multi-layer type color photographic light-sensitive materials thusobtained were exposed in the same manner as in Example 3 and then thelight-sensitive materials thus exposed were developed according to theabove described developing procedures for the coupler-in-emulsion layertype color system.

After development, the ratios 'y /y 'y /y and 'y /y were obtained bymeasuring the densities in the same manner as in Example 3. The resultsare shown in Table 4.

TABLE 4 Compound Amount of containing layer Compound 1 'y/rww 'YG/YW'ynl'yw Control. 1. 28 1. 15 1. 06 6 mg./100 g. gelatin 1. 31 1. 19 1.0760 mg./100 g. gelatin. 1. 68 1. 29 1. 10 600 mg./100 g. gelatin 2. 01 1.54 1. 18 Do 1,500 mg./100 g. 1. 95 1. 55 1. 11

gelatin.

Blue-sensitive layer 200 mgJmol Ag 1. 45 1. 21 1. 09 o 400 mg./mol Ag 1.89 1. 31 1. 11 Yellow filter lay 200/100 g gelatin- 1.38 1. 25 1. 07 Do400/100 1;. gelatin 1. 75 1. 38 1. 12 Intermediate layer- 200/100 g.gelatin. 1. 35 1. 26 1. 08 Do 400/100 g. gelatin- 1. 49 1. 37 1. 09

As can be seen from the results shown in the able above, byincorporating Compound 1 in the above-described layers, the ratios 'y/'y /7 and 'y /q were markedly increased and thus the interimage effectswere increased.

24 EXAMPLE 5 According to the above-described procedures, six types ofmultilayer type color photographic light-sensitive materials for thecoupler-in-developer type color system were prepared.

One of them was prepared as a control sample and the other five have thesame composition as that of the control sample except that each of thecompounds shown in Table 5 was incorporated in the first layer, thesecond layer, and the fourth layer as described above in the amountshown in the table.

The multi-layer type color photographic light-sensitive materials thusobtained were exposed and developed as in Example 1 and also thedensities were measured using the same procedure as in Example 1 toprovide the ratio /y and A log E. The results are shown in Table 5.

As can be seen from the results shown in Table 5, the incorporation ofeach of Compounds 19, 21, 27, 32 and 35 of this invention, the values of'y y and A log E were increased and accordingly the interimage eflectbecame larger.

EXAMPLE 6 According to the above-described procedures 31 types ofmultilayer type color photographic light-sensitive materials forcoupler-in-developer type reversal color system were prepared. One ofthem was prepared as a control sample and the remaining thirty have thesame composition as the control sample except that each of the compoundsshown in Table 6 was incorporated in the bluesensitive silver halideemulsion layer (the fourth layer) in the amount shown in Table 6.

The multi-layer type color photographic light-sensitive materials thusprepared were exposed and developed in the same manner as in Example 2.The densities also were measured in the same manner as in Example 2 toobtain 'y /y and S.

The 'y /'y values and the sensitivity values S thus obtained are shownin Table 6, in which the results obtained using the following controlCompounds A, B and C are shown for comparison:

Compound A (for comparison) Compound B (for comparison) E (I C=.

Compound 0 (for comparison) TABLE 6 Compound Amount 1 'yn/yw S 3Experiment No. 1:

Control 1. 12 100 6 1. 20 101 60 1. 41 103 600 1. 95 110 1,500 1. 90 95200 1. 39 98 400 1. 78 70 200 1. 28 100 400 1.50 98 200 1. 21 105 400 1.48 102 l Mg./mol of blue-sensitive silver halide. 2 Relative sensitivityof hlue-sens1t1ve layer.

In Table 6, Experiment Nos. 1-3 were developed separately. In order thatExperiments 1-3 could be compared with each other, the control samplewas processed in each experiment and the results of the controlexperiment are shown at the top of each experimental group. Since eachof the control experiments were so controlled providing essentially thesame results, these experimental results can be compared directly witheach other.

From the results shown in Table 6, it can be seen that by theincorporation of Compounds 18, 20, 22-24, 29-30. 33-34, and 37-38 ofthis invention, the value of 'y /q was markedly increased and hence theinterimage efi'ect became larger.

Also, from the results shown in Table 6 it can be seen that when thecompound of general Formula I, but where R is a hydrogen atom which isdiiferent from the compound of this invention, that is to say CompoundA, B or C, which can assume the corresponding mercapto form onenolation, the value 'y /y was increased but the sensitivity was greatlyreduced.

As shown above, the compounds of this invention have the advantages thatthe interimage effect becomes larger when they are used unaccompaniedwith any desensitization.

EXAMPLE 7 The multi-layer type color photographic light-sensitivematerials for the coupler-in-developer type color system were exposed inthe same manner as in Example 3. The light-sensitive materials thusexposed were developed according to the above-described developingprocedures for the coupler-in-developer type color system except thateach of the compounds shown in Table 7 was incorporated in the negativedeveloper solution in the amount shown in Table 7. After development,the values of 'y /y 'y /v and 7 /7 were obtained in the same manner asin Example 3. The results thus obtained are shown in Table 7,

1 Mg./liter of negative developer solution.

From the results shown in Table 7, it can be seen that incorporation ofCompounds 18, 21 and 28 of this invention in the negative developersolution, the interimage effect occurred in each of the yellowdye-containing emulsion layer, magenta dye-containing layer, and cyandyecontaining layer.

EXAMPLE 8 According to the above-described procedures, 11 types of themulti-layer type color photographic light-sensitive materials for thecoupler-in-emulsiontype color system were prepared. One of them wasprepared as a control sample and the remaining 10 had the samecomposition as that of the control sample except that Compound 21 wasincorporated in the protective layer (the eighth layer), theblue-sensitive silver halide emulsion layer (the seventh layer), theyellow filter layer (the sixth layer), or the intermediate layer (thefourth layer) in the amount shown in Table 8.

The multi-layer type color photographic light-sensitive materials thusobtained were exposed and developed in the same manner as in Example 4and the densities were measured in the same manner as in Example 4 toobtain the values of 'y y 'y and 'y The results obtained are shown inTable 8.

TABLE 8 Compound- Amount of containing layer Compound 21 ya/7w 'yolywYB/7W Control 0 1.30 1. 18 1. 10 Protective layer: 6 rug/100 g.gelatin. 1. 33 1. 19 1. 11 Do 60 rug/100 g. gelatin 1. 69 1.31 1. 13 Do.600 rug/100 g. gelatin 2. 05 1. 59 1. 20 Do 1,500 mg./l00 g.gelatin. 1. 1. 55 1. 19 Blue-sensitive layer 00 mg./mol Ag 1. 54 1. 25l. 13 D0 400 mg./mol Ag 1. 80 1. 39 1. 18 Yellow filter layer. 200 mg./g. gelatin.. 1. 41 1. 2O 1. 12 o 400 mg./100 g. gelatin 1. 75 1. 36 1.14 Intermediate layer 200 mg./10D g. gelatin 1. 38 1. 21 1. 13 Do 400mg./100 g. gelatin.. 1. 45 1. 28 l. 15

From the results shown above it can be seen that by incorporatingCompound 21, the values of /y 'y /y and 'y /'yw were markedly increased,that is to say, the interimage effect was increased.

EXAMPLE 9 According to the above-described procedures, 11 types of themulti-layer type color photographic light-sensitive materials for thecoupler-in-emulsion layer type color system were prepared. One of themwas prepared as a control sample and the remaining ten have the samecomposition as that of the control sample except that each of thecompounds shown in Table 9 was incorporated in the blue-sensitive silverhalide photographic emulsion layer (the above-described eighth layer).

The multi-layer type color photographic light-sensitive materials thusprepared were exposed in the same manner as in Example 1 and developedin the same manner as in Example 4. Then, the densities were measured asin Example 4 to provide 'y /y The results are shown in Table 9.

TABLE 9 Compound Amount 1 'ynl'yw Control 0 1. 27 Compound 25. 200 1. 38Do 400 1.45

1 Mg./mo1 of silver halide.

:From the results shown in Table 9, it can be seen that theincorporation of Compounds 25, 26, 31, 3S and 36 increased the value of'y /y markedly, that is to say, the interimage effect was increased.

wherein Q represents an atomic group necessary to complete aheterocyclic ring selected from the group consisting of thethiazolidine-2-thion ring series, the imidazolidine-2-thion ring series,the selenazolidine-Z-thion ring series, the 1,3,4-thiadiazline-2-thionring series, the 1,3,4- selenadiazoline-Z-thion ring series, the4-thiazoline-2-thion ring series, the 4-selenazoline-2-thion ringseries, the 1,2- dihydropyridine-2-thion ring series, thebenzthiazoline-Z- thion ring series, the benzoxazoline-Z-thion ringseries, the benzimidazoline-Z-thion ring series, thebenzselenazoline-2-thion ring series and the 1,2-dihydroquinoline-2-thion ring series, wherein R is an alkyl group having 1 to 6 carbonatoms, a hydroxy or an aryl substituted alkyl group, said alkyl grouphaving from 2 to 6 carbon atoms, an aryl group, an alkyl, an alkoxy, ora halogen substituted aryl group, or a Z-pyridyl group.

2. The process as claimed in claim 1, wherein the compound of thegeneral Formula I is selected from the group consisting of compoundshaving the general Formulae Ia, Ib and Ic:

l /o=s B it (Ib) and s "T J wherein X is selected from the groupconsisting of a sulfur atom, an oxygen atom, a selenium atom, a N- groupand a CH=CH-- group; wherein A and B each is selected from the groupconsisting of a hydrogen atom, an alkyl group, a hydroxyl or a halogensubstituted alkyl group, said alkyl group having from 1 to 6 carbonatoms, an aryl group, an alkyl, a hydroxyl or a halogen substituted arylgroup, an alkoxycarbonyl group,.by the combination of the A and B atrimethylene group and a tetramethylene group, and an atomic groupnecessary to complete, by the combination of said A and B, a benzenering and a benzene ring substituted with a member selected from thegroup consisting of an alkyl group, an aryl group, an alkoxyl group, anda halogen atom; wherein Y is selected from the group consisting of analkyl group, an alkoxyl group, and an alkylthio group; and wherein R andR" are selected from the group consisting of an alkyl group having from1 to 6 carbon atoms, a hydroxyl or an aryl substituted alkyl group, saidalkyl group having from 2 to 6 carbon atoms, an aryl group, an alkyl, analkoxy or a halogen substituted aryl group, and a 2-pyridyl group.

3. The process as claimed in claim 2, wherein each of A and B isselected from the group consisting of a hydrogen atom, an alkyl group, ahydroxyl or a halogen substituted alkyl group, said alkyl group havingfrom 1 to 6 carbon atoms, an aryl group, an alkyl, a hydroxyl or ahalogen substituted aryl group, an alkoxycarbonyl group, by thecombination of A and B a trimethylene group and a tetramethylene group,and an atomic group necessary to complete, by the combination of A andB, a benzene ring and a benzene ring substituted with a member selectedfrom the group consisting of an alkyl group, an aryl group, an alkoxylgroup, and a halogen atom; wherein Y is selected from the groupconsisting of a methyl group, an ethyl group, an n-butyl group, ann-hexyl group, a methoxy group, an ethoxy group, a methylthio group, anethylthio group and a 2-(4-phenyl- S-thio- 1 ,3,4-thiadiazoline-2-yl-mercaptoethylthio group.

4. The process as claimed in claim 1, wherein the compound of thegeneral Formula I is incorportaed in at least one of the layers selectedfrom the group consisting of the silver halide emulsion layers of themulti-layer type color photographic light-sensitive material and thelayers adjacent to the silver halide emulsion layers of the multilayertype color photographic light-sensitive material.

5. The process as claimed in claim 1, wherein the compound of thegeneral Formula I is incorporated in a developer solution.

6. The process as claimed in claim 1, wherein at least one of the silverhalide emulsion layers contains a member selected from the groupconsisting of silver chloroiodide, silver iodobromide and silverchloroiodo-bromide, said layer having an iodine content of from 1 to 10molar percent.

7. The process as claimed in claim 1, wherein said processing of themulti-layer type color photographic light-sensitive material is using areversal color system.

8. The process as claimed in claim 7, wherein a dye image is formed bysuccessively developing the light-sensitive material using colordeveloper solutions each containing a ditfusible coupler to be coupledin each different color layer.

9. The process as claimed in claim 7, wherein a dye image is obtained byincorporating each diffusion resisting coupler capable of being coupledin each ditferent color layer in each silver halide emulsion layer ofthe light-sensitive material and processing the light-sensitive materialusing color developer solutions containing no couplers.

10. The process as claimed in claim 1, wherein the compound of thegeneral Formula I has the formula (i in.

11. The process as claimed in claim 1, wherein the compound of thegeneral Formula I has the formula CaHl 29 30 12. The process as claimedin claim 1, wherein the 16. The process as claimed in claim 1, whereinthe compound of the general Formula I has the formula compound of thegeneral Formula I has the formula c=s s H: N

E III AIHI CH: 1 17. The process as claimed in claim 1, wherein the Theprocess as claimed in claim 1, wherein the compound of the generalFormula I has the formula compound of the general Formula I has theformula S HzCS SE=S 1, 15

14. The process as claimed in claim 1, wherein the R Ct 11 compound ofthe general Formula I has the formula eferences l e UNITED STATESPATENTS 2,742,832 4/1956 Salminen 96-74 0:3 2,353,754 7/1944 Peterson96-56 2,652,328 9/1953 Sprung 96-74 N 3,026,201 3/1962 Rauch et a1.96109 5 3,152,905 10/1964 Gaspar 9674 3,161,520 12/1964 Rauch et a1.96109 15. The process as claimed in claim 1, wherein the 3,252,7995/1966 compound of the general Formula I has the formula Gotze et 96-109OH, OTHER REFERENCES I I\ Abbott: Defensive Publication T882,019, J an.26, 1971.

0:5 I. TRAVIS BROWN, Primary Examiner US. Cl. X.R.

